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Green Extraction of Palmitic Acid from Palm Oil using Betaine-Based Natural
Deep Eutectic Solvents

Article  in  International Journal of Technology · April 2018

DOI: 10.14716/ijtech.v9i2.1008

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International Journal of Technology (2018) 2: 335-344
ISSN 2086-9614 © IJTech 2018

GREEN EXTRACTION OF PALMITIC ACID FROM PALM OIL USING

BETAINE-BASED NATURAL DEEP EUTECTIC SOLVENTS

Kamarza Mulia1*, Dezaldi Adam1, Ida Zahrina2, Elsa Anisa Krisanti1

1
Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI
Depok, Depok 16424, Indonesia
2
Department of Chemical Engineering, Faculty of Engineering, University of Riau, Pekanbaru 28293,
Indonesia

(Received: December 2017 / Revised: December 2017 / Accepted: January 2018)

ABSTRACT
In the palm oil refining processes, the free fatty acid content is reduced to an acceptable level by
using steam-stripping that causes, also, the loss of nutraceuticals such as tocopherols and
carotenoids. An alternative method, such as solvent extraction, to separate free fatty acids,
especially palmitic acid as the major free fatty acid present in palm oil, will conserves not only
the important nutraceuticals but, also, conserves energy because a steam requirement is
eliminated. The objective of this research is to evaluate the performance of Natural Deep
Eutectic Solvents (NADES), each consisting of betaine as the hydrogen bonding acceptor and a
polyalcohol as the hydrogen bonding donor, to extract palmitic acid from palm oil. The goal is
to obtain a NADES that is able to extract palmitic acid from palm oil with the highest extraction
yield. The viscosity of various studied NADES was 10-236 cSt while the polarity parameter,
determined by using Nile red as the solvatochromic dye, was 48.9-50.8 kcal/mol. The obtained
data shows that, for NADES having similar polarity to that of betaine, the extraction yields
reduce with increasing viscosity of the NADES. The highest extraction yield of 60% (w/w),
corresponding to a distribution coefficient value of 0.75, was obtained by using NADES
consisting of betaine and 1,2-butanediol. The extraction yield and distribution coefficient values
indicated the potential of NADES, prepared by friendly compounds of betaine and
polyalcohols, as alternative green solvents in the solvent extraction process when separating
free fatty acids from palm oil.

Keywords: Betaine; Deep-eutectic-solvent; Palmitic acid; Palm-oil; Polyalcohol

1. INTRODUCTION
Palm oil is obtained from crude palm oil after going through the degumming, bleaching, and
deacidification processes to get rid of impurities and unwanted components. Palm oil has a
unique composition of saturated and unsaturated fatty acids (50:50) and contains desirable
compounds such as triacylglycerols, tocopherols, tocotrienols, carotenoids and phytosterols
(Edem et al., 2002). Generally, good quality oil contains more than 95% neutral triacylglycerols
and 0.5% or less free fatty acids (Lin, 2002; Mba et al., 2015). The presence of free fatty acids
in palm oil is undesirable because it is easily oxidized and can cause rancidity (Zahrina et al.,
2018).
In some of the palm oil refining processes, valuable nutraceuticals, such as tocopherols and

*Corresponding author’s email: kmulia@che.ui.ac.id, Tel: +62-21-7863516, Fax: +62-21-7863515

Permalink/DOI: https://doi.org/10.14716/ijtech.v9i2.1008
336 Green Extraction of Palmitic Acid from Palm Oil using Betaine-based
Natural Deep Eutectic Solvents
carotenoids, are lost or degraded in the deacidification process because of the chemicals and
high temperature steam (240-260C) used to evaporate the free fatty acids (Hamunen, 2010). It
is preferable to carry out the deacidification process by using a solvent extraction method at
ambient temperature and pressure because it reduces the nutraceutical compounds losses and
reduces the consumption of energy (Gonçalves & Meirelles, 2004, Rodrigues et al., 2007).
However, by using hydrated ethanol as a solvent for the extraction, it turns out that there is an
unacceptable low amount of extracted free fatty acids (Gonçalves et al., 2007).
Rodrigues et al. (2006) reported that free fatty acids could be extracted from cottonseed oil
without reducing the nutraceutical content by using ethanol as extracting solvent. The process
was optimized by adjusting the ethanol/water ratio and extraction temperature. The addition of
water to ethanol solvent can reduce the nutraceutical loss present in cottonseed oil. However,
this process can reduce the palmitic acid content of the palm oil to only 0.3% which is still
higher than the 0.1% representing the upper limit requirement for food products. Therefore, the
search for an alternative solvent for the extraction of free fatty acids from palm oil continues.
Green solvents are widely used as substitutes of hazardous organic solvents in order to
minimize the environmental problems and to improve safety and health and reduce the cost (Bi
et al., 2013). The usage of green solvents in the extraction of natural products is known as green
extraction (Chemat et al., 2012). Ionic Liquids (ILs) are used in a wide range of applications
(Earle & Seddon, 2000; Earle et al., 2006; Han & Row, 2010). However, due to the high
toxicity of some ILs and the high cost of their synthesis, ILs are not commonly used in the
pharmaceutical and food industries (Choi et al., 2011; Angell et al., 2012; Dai et al., 2013a).
Abbott et al. (2004) reported firstly about deep eutectic solvents that had similar physical
properties and phase behaviors to of ILs. Such solvents were regarded as alternatives to ILs due
to their ease of synthesis, availability, biodegradability, negligible volatility, being
environmentally friendly and of low cost (Zhang et al., 2012; Hayyan et al., 2013, Maugeri et
al., 2012). Deep eutectic solvents can be formed by mixing a Hydrogen Bond Acceptor (HBA),
such as a quaternary ammonium salt, as and one or more Hydrogen Bond Donors (HBD) such
as amides, carboxylic acids and polyalcohols. The HBA and HBD form intermolecular
hydrogen bonds with each other when mixed in a certain molar ratio and produce an eutectic
mixture that has a lower melting point than its individual components. Dai et al. (2013b)
reported the existence of Natural Deep Eutectic Solvents (NADES) by using mixtures of
various cellular constituents (primary metabolites) from all kinds of organisms. NADES, which
are still liquid at room temperature, have nontoxic and environmentally friendly characteristics
that are used potentially as solvents for the extraction of bioactive compounds from plants (Bi
et al, 2013; Mulia et al., 2015; Garcia et al., 2016).
In this study, NADES, based on betaine as an HBA combined with various polyalcohols as
HBDs, were used as a green solvent to extract free palmitic acid (representing the free fatty
acids) from palm oil. The objective was to determine the composition of NADES that would be
able to extract palmitic acid from palm oil with a high extraction yield and a high distribution
coefficient. The ability of betaine-based NADES to extract palmitic acid was investigated by
varying the type of polyalcohols as HBDs and the mole ratio of the betaine to polyalcohol. The
amount of palmitic acid extracted into NADES and the physicochemical properties of the
NADES, such as viscosity, polarity, and density, were determined.

2. MATERIALS AND METHODS

2.1. Chemicals
Synthesis grade palmitic acid (purity 99%) was purchased from Merck. Palm oil (analytical
grade), carotene (synthesis grade), tocopherol (synthesis grade), and glycerol (analytical grade)
Mulia et al. 337

were purchased from Sigma Aldrich. Ethanol and ethylene glycol (analytical grade) were
purchased from Merck. Anhydrous betaine (>98%), synthesis grade 1,2-propanediol, 1,3-
propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol were purchased from Tokyo
Chemical Industry (TCI). Figure 1 below shows the molecular structure of betaine,
polyalcohols and palmitic acid.

(1) Palmitic acid (2) Betaine

(3) 1,2-propanediol (4) 1,3-propanediol

(5) 1,2-butanediol (6) 1,3-butanediol

(7) 1,4-butanediol (8) Ethylene Glycol

(9) Glycerol

Figure 1 Chemical structure of palmitic acid, betaine and polyalcohols used

2.2. Preparation of NADES and Mixture of Palm Oil

The preparation of NADES followed the procedure reported by Dai et al. (2013b). Betaine was
mixed with each of the following polyalcohols: 1,2-propanediol, 1,3-propanediol, 1,2-
butanediol, 1,3-butanediol, 1,4-butanediol, ethylene glycol, and glycerol; in molar ratios of 1:3,
1:4 and 1:5 respectively. A synthetic palm oil mixture was prepared according to the procedure
reported by Zahrina et al. (2018); this replicates the composition of the palm oil available
commercially. Mild heating was used to keep the palm oil in a liquid phase and the mixing
process temperature low in order to avoid degradation of the organic materials.
2.3. Extraction Process
The palm oil mixture was mixed with NADES in a mass ratio of 1:2 (w/w) at 50°C and stirred
at 500 rpm for 3 h. The extraction was carried out in a sealed tube to prevent evaporation. The
extraction temperature was kept low because, at higher temperatures, the nutriceutical
compounds in palm oil, carotene and tocopherol, degrade and damage. The separation process
of extracts was carried out by using centrifugation at this temperature for one hour with
agitation of 3000 rpm. The temperature was kept, also, at 50C during separation in order to
prevent the solidification of palm oil (Israyandi et al, 2017; Zahrina et al., 2018).
2.4. Palmitic Acid Content, Extraction Yield and Distribution Coefficient
The amount of palmitic acid, absorbed into NADES, is considered to be equivalent to the
amount of free fatty acids absorbed into NADES. The content of palmitic acid in NADES was
determined based on the amount of palmitic acid that remained in the palm oil. The quantity of
palmitic acid was determined by acid-base titration using potassium hydroxide. The palm oil
338 Green Extraction of Palmitic Acid from Palm Oil using Betaine-based
Natural Deep Eutectic Solvents
was separated from NADES by washing the mixture with aquadest at 80°C and using a funnel
separator several times. Jones’ reagent was used to test the presence of NADES in the water
used for washing. The palm oil, separated from NADES, was diluted in ethanol and, then, was
titrated with potassium hydroxide until the phenolphtalein indicator turned light purple (Zahrina
et al., 2018). The titration of the palm oil was carried in a heated flask and stirred to keep the
palm oil as a liquid. As in Equation 1 below, the palmitic acid extraction yield was calculated as
the percent ratio of the mass of extracted palmitic acid to the mass of palmitic acid present
initially in the palm oil.

(1)

The tendency of palmitic acid to transfer to the NADES phase rather than remaining in palm oil
phase is expressed in Equation 2 below as a distribution coefficient (K) in mg/ml (NADES
phase/Oil phase).

(2)
2.5. Polarity Parameter Measurement
The polarity of NADES, used in this study, is represented as its polar parameter calculated from
the solvatochromic shift of the Nile red dye obtained by using UV-visible spectrophotometry in
the 400-700 nm range (Ogihara et al., 2004). By using a Spectroquant Pharo 300 model
spectrophotometer, the polarity parameter value, based on solvatochromic shift, was measured
according to the procedure, reported by Dai et al. (2013a), at room temperature. As shown in
Equation 3 below, the polarity parameter of a sample using Nile red dye absorbance was
calculated as molar transition energy (ENR) (Reichardt, 1994):

(3)

where max was the wavelength at the maximum absorbance and was measured in triplicate
runs. It is recognized that the higher the polarity of a solvent, the higher its ENR value. The
concentration of the Nile red dye and the sample in the solvent was set in the range of 10 -410-5
M to reduce the interaction of visible solutes (Harris, 2008). Nile red dye is soluble in ethanol
and NADES gives a pink color to the solution. The λmax observed in the UV-spectrum of the
Nile red dye shifts towards a lower wavelength in a more polar solvent (Fletcher et al., 2001),
and, hence, according to Equation 3, a more polar compound is indicated by a higher ENR value.
2.6. Viscosity and Density Measurement
The viscosity of the NADES was measured by using a Cannon-Fenske Viscometer 200 and 350
suitable for 20-100 cSt and 100-500 cSt ranges, respectively. The viscosity readings were
obtained by passing samples through the cavity pipe in a water bath with a controlled
temperature. The density of NADES was determined by using an Anton-Parr densitometer. The
ionized water was used for calibrating the viscometer and the densitometer. Relative density is
the ratio between the density of the substance at a given temperature to the density of the water
at the same temperature. As the reference fluid, the density of NADES and water was measured
at 40C. For each NADES, the viscosity and density were measured in triplicate runs.
Mulia et al. 339

3. RESULTS AND DISCUSSION

3.1. NADES Preparation
In this work, NADES consisting of betaine with seven types of polyalcohols as HBDs and in
three molar ratios of betaine to HBDs, were tested and the results are given in Table 1. The
stable NADES was formed when the mixture was a clear and viscous liquid and without
precipitation. It was found that the preparation time required to gain a homogenous and stable
mixture was different for each composition. The chemical structure of HBD and physical
characteristics seem to play an important role in the formation and stability of the NADES. The
formation of a stable mixture of the HBA and HBD is indicated by the depression of the
freezing point relative to pure compounds (Abbott et al., 2004; Harris, 2008). The time required
to form a stable mixture relates to the energy required to lower the freezing point of each
compound in order to obtain a lower freezing point of the mixture., As a HBA, betaine is a solid
solution at room temperature and has a melting point (freezing point) of 301°C, while the
polyalcohols are liquids. Among the polyalcohols used as HBDs, 1,4-butanediol has the highest
freezing point of 20.1C. Therefore the time required to form stable NADES, made of betaine
and 1,4-butanediol, was the longest.

Table 1 Composition, formation time and physical properties of betaine based NADES
Stable
Polarity
HBD (polyalcohol) in Betaine: HBD NADES Viscosity Density
parameter
Betaine-NADES molar ratio formed (cSt) (g/ml)
ENR (kcal/mol)
(days)
1:3 7 44.7 49.57 1.070
1,2-propanediol 1:4 1 47.1 49.59 1.066
1:5 1 24.2 50.60 1.064
1:3 8 34.8 48.92 1.075
1,3-propanediol 1:4 1 37.8 50.69 1.072
1:5 1 9.7 48.92 1.065
1:3 17 25.0 50.43 1.050
1,2-butanediol 1:4 1 37.3 50.29 1.043
1:5 1 32.0 50.34 1.036
1:3 21 43.9 49.72 1.051
1,3-butanediol 1:4 2 52.4 49.68 1.044
1:5 1 17.0 49.90 1.035
1:3 24 51.6 50.51 1.054
1,4-butanediol 1:4 8 23.5 50.56 1.050
1:5 5 41.3 50.78 1.043
1:3 6 151.0 49.47 1.205
Glycerol 1:4 4 236.0 49.51 1.224
1:5 2 93.7 49.59 1.229
1:3 1 10.0 50.03 1.120
Ethylene glycol 1:4 1 39.4 50.29 1.126
1:5 1 13.2 50.34 1.122
340 Green Extraction of Palmitic Acid from Palm Oil using Betaine-based
Natural Deep Eutectic Solvents
During the preparation process, it was found that, when the mole ratio of betaine to
polyalcohols was 1:3, a longer chain of polyalcohols required a longer time to form stable
NADES. The time required for stable NADES of 1,2 propanediol, 1,3-propanediol, glycerol
and ethylene glycol was shorter when compared to the time for all butanediols NADES. This is
consistent with Dai et al.’s (2013a) studies that the spatial structure of HBDs affected the
stability and characteristic of NADES. However, when the mole fraction of polyalcohols was
increased, the time required to form stable NADES became similar. As occurs between choline-
chloride and polyalcohols, the formation of NADES can be affected by the formation of
hydrogen bonds between betaine and polyalcohols (Harris, 2018). The electronegativity
difference between oxygen atoms with betaine and hydrogen atoms of hydroxyl groups in
polyalcohol is preferable for the formation of hydrogen bonds (Dai et al, 2013a).
3.2. Physical Properties of NADES
The polarity of NADES was represented by the polar parameter ENR, obtained from
solvatochromic shift of the Nile red dye. The λmax, observed in the UV-spectrum of the Nile red
dye, shifts towards a lower wavelength in a more polar solvent (Fletcher et al., 2001) and,
hence, according to Equation 1, a more polar compound has a higher ENR value. Table 1 data
indicated that the change of molar ratios of betaine to polyalcohol of 1:3 to 1:5 did not have
much effect on the polarity of solvents which was represented by the values of ENR in the range
of 48.9250.78 kcal/mol.
It was reported previously that the polarity of NADES related to the hydrogen bonds that
occurred between HBD and HBA, either intermolecular or intramolecular. Therefore, the
formation of more hydrogen bonds caused higher polarity of the solvent. However, the result of
a recent study was not consistent with the previous study, using choline chloride as HBA with
1,3-butanediol as HBD, where increased amounts of choline chloride increased the polarity of
the solvent (Harris, 2008). The possible explanation for this observed data is that the polarity
and molar volume of pure betaine are much higher than those of polyalcohols used as HBD.
Consequently, even although the amount of polyalcohols increased in NADES, there was no
significant change in the polarity.
As shown in Table 1, the viscosities of the NADES, at the molar ratio betaine to HBD from 1:3
to 1:5 were measured, and the highest viscosity was found in the 1:4 molar ratio. Increasing the
amount of HBD in the solvent might increase the size of ionic species due to the formation of
hydrogen bonds between HBD and HBA and, hence, might reduce either its ability to flow or
increase the viscosity. However, further increases to the amount of HBD might reduce the
strength of hydrogen between HBD and HBA and, therefore, the free volume of solvent might
increase and the viscosity might be reduced. This explanation is in agreement with the Abbot et
al.’s (2004) and Harris’ (2008) statements that the presence of HBA-HBD hydrogen bonding
and the free volume affected the viscosity of DESs.
Table 1 also shows that the densities of NADES, prepared from betaine with 1,2-propanediol,
1,2-butanediol, 1,3-butanediol and 1,4-butanediol, increased with the increased betaine-to-
polyalcohols mole ratio (from 1:5 to 1:3) in NADES. This study’s observation of density was in
accordance with the density reported for choline chloride based DESs. This was associated with
the presence of the free volume in DESs and, hence, the increase of the salt ions-to-polyalcohols
molar ratios reduced the free volume and increased the density of the DESs (Harris, 2008).
3.3. Extraction of Palmitic Acid into NADES
After mixing palm oil and NADES for 3 hours, palm oil and NADES were centrifuged to
separate NADES from palm oil. Due to the differences in their density, NADES and oil phase
were separated as lower and upper phases respectively. The NADES’ color was more intense
since it contained more palmitic acid than the oil phase. The palm oil-NADES emulsion took a
Mulia et al. 341

longer time to separate for the butanediol-NADES that had a high viscosity value. The
separation time of the glycerol-NADES was the longest due to palm oil’s difficulty in diffusing
within the highly viscous betaine-glycerol NADES. As in Equation 1, the palmitic acid
extraction yield was calculated as the percent ratio of the mass of extracted palmitic acid to the
mass of palmitic acid present initially in the palm oil. Figure 2 shows the different yields of
single-stage extraction of palmitic acid by using different polyalcohol as HBD in betaine based
NADES. All tested betaine-polyalcohol NADESs extracted palmitic acid from palm oil with
more than 30% (w/w). The highest yield of 60% (w/w) was obtained by using betaine-1,2-
butanediol NADES at an oil-to-solvent volume ratio of 1:2, temperature of 40°C and 5.6% mass
of palmitic acid in the palm oil feed. The variation of mole ratios from 1:3 to 1:5 for the betaine
and 1,2-butanediol NADES did not show many differences in the extraction yields . The
palmitic acid extraction yield, reported in this study, is higher than the 49% (w/w) yield
obtained previously by Zahrina et al. (2018) using the betaine monohydrate and 1,2-propanediol
NADES.

Figure 2 Palmitic acid xxtraction yield in various NADES with betaine to-HBD mole ratios
1:3 to 1:5

Although, 1,2 propanediol and 1,2-butanediol HBDs with molar ratio 1:3 have similar positions
of hydroxyl groups, the viscosity of 1,2 propanediol is higher than 1,2-butanediol NADES
(Table 1). This causes the extraction yield of 1,2-butanediol NADES to be higher than 1,2-
propanediol NADES at a similar molar ratio of 1:3. This result may be because of the larger
free volume of 1,2-butanediol, with longer chain, than 1,2-propanediol in betaine NADES.
Viscosity data in Table 1 and extraction yield in Figure 2 indicate that viscosity is not the only
factor affecting the extraction. This is exemplified by the similar extraction yields obtained
using viscous NADES with glycerol HBD, and less viscous NADES with ethylene glycol HBD.
Glycerol has three hydroxyl groups and, with a shorter chain, ethylene glycol has only two
hydroxyl groups. It seems that, in NADES, the spatial structure of these HBDs hinders the
interaction of extracted compounds with solvent molecules. Harris (2008) reported similar
results reported by using choline chloride based NADES.
Another important factor in solvent extraction is the match between the polarity of the solvent
and the compound to be extracted. The measured ENR of palmitic acid was 51.84 kcal/mole,
similar to those of NADES containing 1,2-butanediol, 1,4-butanediol, and ethylene glycol as
HBD (Table 1). It was noted that, when extraction yields of these NADES were plotted against
their viscosities, a consistent declining trend was observed as shown in Figure 3. It appeared
that the effect of viscosity was significant when the polarity parameter of the used palmitic acid
and NADES were similar. The betaine-ethylene glycol NADES’ lower ability to extract
palmitic acid might be caused by the spatial effect. The adjacent two hydroxyl groups in
ethylene glycol caused the NADES structure to become tight and rigid with limited of free
342 Green Extraction of Palmitic Acid from Palm Oil using Betaine-based
Natural Deep Eutectic Solvents
volume. In contrast, 1,2-butanediol had an ethyl branch that enabled the NADES structure to
have the unrigid conformation and let the palmitic acid diffuse and interact with the betaine.
Harris (2008) reported similar situations when using NADES with choline chloride as a
quaternary ammonium salt.
In the extraction process using NADES, the intermolecular formation of hydrogen bonds of the
hydroxyl group of the HBD compete with the ionic oxygen of HBA and the formation of
hydrogen bonds between the extracted compound compete with the ionic species of NADES.
As explained in Equation 2, the tendency of palmitic acid to transfer to the NADES phase rather
than remaining in the palm oil phase is expressed as a distribution coefficient of K in mg/mL
(NADES phase/Oil phase).

70
Palmitic acid extraction yield

60

50
(%-w/w)

40

30

20 1,2-butanediol as HBD
ethylene glycol as HBD
10 1,4-butanediol as HBD
0
0 10 20 30 40 50 60
Viscosity of NADES in cSt

Figure 3 Palmitic acid extraction yield against viscosity of NADES with similar ENR values

The higher tendency to remain in the NADES phase rather than in oil phase show higher values
of K and vice versa. Figure 4 shows that the use of different polyalcohol as HBD with betaine,
in different molar ratios, resulted in a different distribution coefficient. The highest distribution
coefficient of 0.75 was obtained by using 1,2-butanediol in betaine mixture. This related to 60%
(w/w) yield in a single-stage extraction of palmitic acid with an oil-to-solvent volume ratio of
1:2. This result indicated that NADES, prepared by mixing 1,2-butanediol with betaine, could
be used to extract palmitic oil from palm oil.

Figure 4 Distribution coefficient of palmitic acid in NADES phase/oil phase (NADES with
betaine to-polyalcohol mole ratios 1:3 to 1:5)

4. CONCLUSION
The physicochemical properties of betaine-polyalcohol NADES and the molecular structure of
polyalcohols affected the stability and performance of NADES extracting palmitic acid from
Mulia et al. 343

palm oil. The viscosity and density of NADES from betaine and polyalcohols appeared to be
influenced by the type of polyalcohols and the molar ratios of betaine-to-polyalcohols. The
hydrogen bonds and free volume formation were expected to affect the value of viscosity and
density. The polarity of the studied NADES was more likely to be affected by the type of
polyalcohol used rather than by the molar ratio of betaine-to-polyalcohol. There is relationship
between the extraction yield and viscosity, for NADES with closed polarity (ENR) to the
polarity of pure betaine, i.e. the extraction yield declines with increasing viscosity of the
NADES. The highest single-stage extraction yield of palmitic acid from palm oil was 60%
(w/w) with the distribution coefficient of 0.75; this was obtained by using NADES from betaine
and 1,2-butanediol. This study’s extraction condition was mild and each NADES was prepared
from environmentally friendly compounds that were less or non-toxic to human or living things.
The results indicate that NADES, prepared by friendly compounds of betaine and polyalcohols,
have the prospect of being alternative green solvents in separating free fatty acids from palm
oils in the solvent extraction process.

5. ACKNOWLEDGEMENT
The authors are grateful for the Universitas Indonesia’s financial support through the DRPM
PITTA project, contract number 772/UN2.R3.1/HKP.05.00/2017.

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